CN1611557A

CN1611557A - Phase change inks containing colorant compounds

Info

Publication number: CN1611557A
Application number: CNA2004100620509A
Authority: CN
Inventors: 吴波; J·H·班宁; J·M·杜夫; W·G·韦勒; D·R·蒂特林顿
Original assignee: Xerox Corp
Current assignee: Xerox Corp
Priority date: 2003-06-26
Filing date: 2004-06-25
Publication date: 2005-05-04
Anticipated expiration: 2024-06-25
Also published as: CN100497498C; JP5021893B2; US6860931B2; EP1491596A1; MXPA04006264A; BRPI0402524B1; EP1491596B1; CA2472113C; BRPI0402524A; JP2005015809A; US20050016417A1; CA2472113A1

Abstract

Phase change inks are disclosed comprising a carrier and a colorant of the formula wherein R₁，R₂，R₃，R₄，R₅，R₆，R₇，a，b，c，d，Y，Q，Q^－The definitions of A, and CA are as described in the specification.

Description

The phase change ink that contains colorant compound

Technical field

The present invention relates to phase change ink.More specifically, the present invention points to hot melt or the phase change ink that comprises the specific colorants compound.

Background technology

Although known composition and technology are fit to its intended purposes, but need new pinkish red dye compositions, particularly be applicable to the pinkish red dye compositions of phase change ink, pinkish red tinting material with ideal thermostability, the pinkish red tinting material that when being exposed to the temperature of rising, presents minimum non-required variable color, pinkish red tinting material with ideal brightness, pinkish red tinting material with ideal tone, pinkish red tinting material with ideal colourity, has the pinkish red tinting material of high light-fast fastness characteristic ideally, has the pinkish red tinting material of pleasant color ideally, the pinkish red tinting material that in the phase change ink carrier composition, has the ideal dissolubility property, can make phase change ink at the pinkish red tinting material that keeps thermostability above injection under 135 degrees centigrade the temperature simultaneously, can make phase change ink produce the pinkish red tinting material of image with low piling height, can make phase change ink produce the pinkish red tinting material that approaches the image of picture quality near lithography, pinkish red tinting material with oxidative stability, sedimentary pinkish red tinting material from phase change ink carrier not, do not diffuse into the pinkish red tinting material of the adjacent printing-ink of different colours in the time of in being included in phase change ink, not from medium such as phase change ink carrier leaching to binder tape, paper, or the pinkish red tinting material of analogue, the pinkish red tinting material that does not cause the phase change ink jet print head to stop up in the time of in being introduced into phase change ink, the image that phase change ink is produced has along with the time keeps the pinkish red tinting material of sharp edge clearly, the pinkish red tinting material that keeps the image of its high image quality when making phase change ink be created in warm climate, phase change ink is produced have the pinkish red tinting material of the image of high optical density (OD) ideally, have low piling height but can not lose the pinkish red tinting material of the image of high optical density (OD) ideally and can make the effective pinkish red tinting material of printing ink cost owing to its good solubility in phase change ink carrier produces.

Summary of the invention

The present invention relates to comprise the phase change ink of following formula colorant compound

With

R wherein ₁, R ₂, R ₃, and R ₄Be respectively (i) hydrogen atom independently of each other, (ii) has at least 1 carbon atom in some embodiments, 2 carbon atoms, 6 carbon atoms, 8 carbon atoms or 18 carbon atoms, have in some embodiments and be no more than 55 carbon atoms, the alkyl group of 30 carbon atoms or 20 carbon atoms (comprises straight chain, side chain, saturated, unsaturated, ring-type, replace, with the unsubstituted alkyl group, wherein can maybe can not there be heteroatoms in the alkyl group, as oxygen, nitrogen, sulphur, silicon, phosphorus etc.), but the number of carbon atom can be outside these scopes, (iii) have at least 6 carbon atoms in some embodiments, 10 carbon atoms or 14 carbon atoms, have in some embodiments and be no more than 26 carbon atoms, the aromatic yl group of 22 carbon atoms or 18 carbon atoms (comprises aromatic yl group unsubstituted and that replace, wherein in aromatic yl group, can have maybe and can not have heteroatoms, as oxygen, nitrogen, sulphur, silicon, phosphorus etc.), but the number of carbon atom can be outside these scopes, (iv) have at least 7 carbon atoms in some embodiments, 12 carbon atoms or 18 carbon atoms, have in some embodiments and be no more than 55 carbon atoms, (comprise aromatic yl alkyl group unsubstituted and that replace, wherein the moieties aromatic yl alkyl group can be a straight chain to the aromatic yl alkyl group of 30 carbon atoms or 20 carbon atoms, side chain, saturated, unsaturated, and/or cyclic, heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus and similar atom can or can not be present among one of the moieties of aromatic yl alkyl group and aryl moiety or both), but the number of carbon atom can be outside these scopes, as benzyl etc., or (v) have at least 7 carbon atoms in some embodiments, 12 carbon atoms or 18 carbon atoms and have in some embodiments and be no more than 55 carbon atoms, the kiki fang alkyl group of 30 carbon atoms or 20 carbon atoms (comprises kiki fang alkyl group unsubstituted and that replace, wherein the moieties of kiki fang alkyl group can be a straight chain, and side chain is saturated, unsaturated, and/or cyclic and heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus, with can or can not be present among one of the moieties of kiki fang alkyl group and aryl moiety or both with similar atom), but the number of carbon atom can be outside these scopes, as tolyl etc., wherein R ₁And R ₂Can be combined together to form ring, wherein R ₃And R ₄Can be combined together to form ring and R wherein ₁, R ₂, R ₃, and R ₄Can be connected respectively on the benzyl ring in the division center, a and b are respectively integer 0,1,2 independently of each other, or 3, c is an integer 0,1,2,3, or 4, each R ₅, R ₆And R ₇Be that (i) has at least 1 carbon atom in one embodiment independently of each other; have in some embodiments and surpassing 50 carbon atoms; the alkyl group of 30 carbon atoms or 18 carbon atoms (comprises straight chain; side chain; saturated; unsaturated; ring-type; replace; with the unsubstituted alkyl group; heteroatoms wherein; as oxygen, nitrogen, sulphur; silicon; atoms such as phosphorus can or can not be present in the alkyl group), but the number of carbon atom can (ii) have at least 6 carbon atoms in one embodiment outside these scopes; have in some embodiments and be no more than 55 carbon atoms; the aromatic yl group of 30 carbon atoms or 18 carbon atoms (comprises unsubstituted and the aromatic yl group that replaces and heteroatoms wherein, as oxygen; nitrogen; sulphur, silicon, atoms such as phosphorus can or can not be present in the aromatic yl group); but the number of carbon atom can be outside these scopes; (iii) have at least 7 carbon atoms in one embodiment and have in some embodiments and be no more than 55 carbon atoms, the aromatic yl alkyl group of 30 carbon atoms or 18 carbon atoms (comprises aromatic yl alkyl group unsubstituted and that replace; wherein the moieties of aromatic yl alkyl group can be a straight chain; side chain is saturated undersaturated, and/or cyclic and heteroatoms wherein; as oxygen; nitrogen, sulphur, silicon; phosphorus; can or can not be present among one of the alkyl of aromatic yl alkyl group and aryl moiety or both with similar atom), but the number of carbon atom can be outside these scopes, as benzyl or analogue; (iv) have at least 7 carbon atoms in one embodiment; have in some embodiments and be no more than 55 carbon atoms, (comprise kiki fang alkyl group unsubstituted and that replace, wherein the moieties of kiki fang alkyl group can be a straight chain to the kiki fang alkyl group of 30 carbon atoms or 18 carbon atoms; side chain; saturated, unsaturated, and/or cyclic; heteroatoms wherein; as oxygen, nitrogen, sulphur; silicon; phosphorus and similar atom can or can not be present among one of the moieties of kiki fang alkyl group and aryl moiety or both), but the number of carbon atom can be outside these scopes; as tolyl or analogue; (v) halogen atom, as fluorine, chlorine; bromine; iodine, or analogue, (vi) ester group; (vii) amide group; (viii) sulfuryl group, (ix) amine groups or ammonium group, (x) nitrile group; (xi) nitryl group; (xii) oh group, (xiii) cyano group, (xiv) pyridine or pyridine group; (xv) ether group; (xvi) aldehyde group, (xvii) ketone groups, (xviii) carbonyl group; (xix) thiocarbonyl group; (xx) sulfate group, (xxi) nitroso-group group, (xxvii) carboxyl groups; (xxviii) anhydride group; (xxix) azide group, (xxx) azo group, (xxxi) cyanate radical closes group; (xxxii) isocyano group; (xxxiii) thiocyanato group, (xxxiv) isothiocyanate bonding group, (xxxv) urethane groups; or (xxxvi) urea groups, wherein R ₅, R ₆, and R ₇Can be connected respectively on the benzyl ring in the division center,

Be

Or

R ₈, R ₉, and R ₁₀Be respectively (i) hydrogen atom independently of each other, (ii) has at least 1 carbon atom in some embodiments, 2 carbon atoms, 6 carbon atoms, 8 carbon atoms or 18 carbon atoms, have in some embodiments and be no more than 55 carbon atoms, the alkyl group of 30 carbon atoms or 20 carbon atoms (comprises straight chain, side chain, saturated, unsaturated, ring-type, replace, with the unsubstituted alkyl group, heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus, can or can not be present in the alkyl group with similar atom), but the number of carbon atom can be outside these scopes, (iii) have at least 6 carbon atoms in some embodiments, 10 carbon atoms or 14 carbon atoms, have in some embodiments and be no more than 26 carbon atoms, the aromatic yl group of 22 carbon atoms or 18 carbon atoms (comprises aromatic yl group unsubstituted and that replace, heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus, can or can not be present in the aromatic yl group with similar atom), but the number of carbon atom can (iv) have at least 7 carbon atoms in some embodiments outside these scopes, 12 carbon atoms or 18 carbon atoms, have in some embodiments and be no more than 55 carbon atoms, (comprise aromatic yl alkyl group unsubstituted and that replace, wherein the moieties of aromatic yl alkyl group can be a straight chain to the aromatic yl alkyl group of 30 carbon atoms or 20 carbon atoms, side chain, saturated, unsaturated, and/or cyclic, heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus and similar atom can or can or can not be present in the aromatic yl group), but the number of carbon atom can be outside these scopes, as benzyl or analogue, or (v) have at least 7 carbon atoms in some embodiments, 12 carbon atoms or 18 carbon atoms and have in some embodiments and be no more than 55 carbon atoms, the kiki fang alkyl group of 30 carbon atoms or 20 carbon atoms (comprises kiki fang alkyl group unsubstituted and that replace, wherein the moieties of kiki fang alkyl group can be a straight chain, and side chain is saturated, unsaturated, and/or cyclic and heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus, can or can not be present among one of the moieties of kiki fang alkyl group and aryl moiety or both with similar atom), but the number of carbon atom can be outside these scopes, and as tolyl or analogue, prerequisite is R in some embodiments ₁+ R ₂+ R ₃+ R ₄+ R ₅+ R ₆+ R ₇+ R ₈+ R ₉+ R ₁₀In the number of carbon atom be at least 16,18,20,22,24,26,28,30,32,34,36,38,40,42,44,46,48,50,52,54,56,58,60,62,64,66,68,70 or 72, each Q is COOH group or SO independently of each other ₃H group, each Q are COO independently of each other ^-Group or SO ₃ ^-Group, d are integers 1,2,3,4, or 5, A is a negatively charged ion, wherein suitable anionic example includes, but is not limited to Cl ^-, Br ^-, I ^-, HSO ₄ ^-, HSO ₃ ^-, SO ₄ ^2-, SO ₃ ^2-, CH ₃SO ₃ ^-, CH ₃C ₆H ₄SO ₃ ^-, NO ₃ ^-, HCOO ^-, CH ₃COO ^-, H ₂PO ₄ ^-, HPO ₄ ^2-, SCN ^-, BF ₄ ^-, ClO ₄ ^-, SSO ₃ ^-, PF ₆ ^-, SbCl ₆ ^-, or analogue, as its mixture and CA be hydrogen atom or with all Q of bar one ^-Group bonded positively charged ion, wherein suitable cationic example includes, but is not limited to alkali metal cation, as Li ⁺, Na ⁺, K ⁺, Rb ⁺, and Cs ⁺, non-polymer or ammonium monomer and quaternary ammonium cation comprise those with following general formula

Each R wherein ₂₁, R ₂₂, R ₂₃, and R ₂₄Be (i) hydrogen atom independently of each other, (ii) has at least 1 carbon atom in some embodiments, 2 carbon atoms, 6 carbon atoms, 8 carbon atoms or 18 carbon atoms, have in some embodiments and be no more than 55 carbon atoms, the alkyl group of 30 carbon atoms or 20 carbon atoms (comprises straight chain, side chain, saturated, unsaturated, ring-type, replace, with the unsubstituted alkyl group, heteroatoms wherein, as oxygen, nitrogen, sulphur silicon, phosphorus, can or can not be present in the alkyl group with similar atom), but the number of carbon atom can be outside these scopes, (iii) have at least 6 carbon atoms in some embodiments, 10 carbon atoms or 14 carbon atoms, have in some embodiments and be no more than 26 carbon atoms, the aromatic yl group of 22 carbon atoms or 18 carbon atoms (comprises aromatic yl group unsubstituted and that replace, heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus, can or can not be present in the aromatic yl group with similar atom), but the number of carbon atom can be outside these scopes, (iv) have at least 7 carbon atoms in some embodiments, 12 carbon atoms or 18 carbon atoms and have in some embodiments and be no more than 55 carbon atoms, the aromatic yl alkyl group of 30 carbon atoms or 20 carbon atoms (comprises aromatic yl alkyl group unsubstituted and that replace, wherein the moieties of aromatic yl alkyl group can be a straight chain, and side chain is saturated, unsaturated, and/or cyclic and heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus, can or can not be present among one of the moieties of aromatic yl alkyl group and aryl moiety or both with similar atom), but the number of carbon atom can as benzyl or analogue, or (v) have at least 7 carbon atoms in some embodiments outside these scopes, 12 carbon atoms or 18 carbon atoms, have in some embodiments and be no more than 55 carbon atoms, (comprise kiki fang alkyl group unsubstituted and that replace, wherein the moieties of kiki fang alkyl group can be a straight chain to the kiki fang alkyl group of 30 carbon atoms or 20 carbon atoms, side chain, saturated, unsaturated, and/or cyclic, heteroatoms wherein, as oxygen, nitrogen, sulphur, silicon, phosphorus and similar atom can or can not be present among one of the moieties of kiki fang alkyl group and aryl moiety or both), but the number of carbon atom can be outside these scopes, as tolyl or analogue, wherein one or more R ₂₁, R ₂₂, R ₂₃, and R ₂₄The alkyl that can be combined together to form ring and wherein replace, aryl; substituting group on arylalkyl and the kiki fang alkyl group can be (but being not limited to) oh group, halogen atom; amine groups, imine group, ammonium group; cyano group pyridine group, pyridine group, ether group; aldehyde group, ketone groups, ester group; amide group, carbonyl group, thiocarbonyl group; sulfate group, sulfonate groups, sulfonic acid group; sulfide group, sulfoxide radicals, phosphine groups; the phosphorus group, phosphate group, nitrile group; mercapto groups, nitryl group, nitroso-group group; sulfuryl group; carboxyl groups, anhydride group, azide group; azo group; cyanate radical closes group, isocyano group, thiocyanato group; isothiocyanate bonding group; carboxylate groups, hydroxy-acid group, urethane groups; urea groups; its mixture, and analogue, wherein two or more substituting groups can be combined together to form ring; oligopolymer and polymer cation; as cationic polymers or oligopolymer, and analogue, with and composition thereof.

In some embodiments, R ₁+ R ₂+ R ₃+ R ₄In the number of carbon atom be at least 16,18,20,22,24,26,28,30,32,34,36,38,40,42,44,46,48,50,52,54,56,58,60,62,64,66,68,70 or 72.

Because heteroatoms can be included in alkyl, aryl in arylalkyl and the kiki fang alkyl group and because these groups can replace, is appreciated that R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉, and R ₁₀Also alkoxyl group, the polyalkylene oxide base, aryloxy, polyarylene oxygen base, arylalkyl oxygen base, poly-aryl alkylene oxygen base, alkylaryloxy, or the group of poly-alkyl arylene oxygen base group and so on, prerequisite is that the Sauerstoffatom in this group directly is not keyed to the nitrogen in the following division center, oxygen, or on the sulphur atom

R wherein _1-4One of group is that the example of the situation of cycloalkyl is

Or

Be

With

R wherein _1-4The example that group is combined into the situation of ring is

Or

Be

With

R wherein _1-4The example that one of group is attached to the situation on the phenyl ring in the division center is

Or

Be

With

In a particular, negatively charged ion A has structural formula A ₁-R ₁₁-A ₂Organic two negatively charged ion, A wherein ₁And A ₂Be anionic group independently of each other respectively, as carboxylate salt, sulfonate, or analogue and R wherein ₁₁Be that (i) has at least 1 carbon atom in some embodiments, 2 carbon atoms, 6 carbon atoms; 8 carbon atoms or 18 carbon atoms and have in some embodiments and be no more than 55 carbon atoms, the alkylidene group of 30 carbon atoms or 20 carbon atoms (comprises straight chain; side chain is saturated, unsaturated; ring-type, alkylidene group replacement and unsubstituted; heteroatoms wherein, as oxygen, nitrogen; sulphur, silicon, phosphorus; can or can not be present in the alkylidene group with similar atom), but the number of carbon atom can (ii) have at least 6 carbon atoms in some embodiments outside these scopes; 10 carbon atoms or 14 carbon atoms and have in some embodiments and be no more than 26 carbon atoms, the arylene group of 22 carbon atoms or 18 carbon atoms (comprises arylene group unsubstituted and that replace; heteroatoms wherein, as oxygen, nitrogen; sulphur, silicon, phosphorus; can or can not be present in the arylene group with similar atom), but the number of carbon atom can (iii) have at least 7 carbon atoms in some embodiments outside these scopes; 12 carbon atoms or 18 carbon atoms and have in some embodiments and be no more than 55 carbon atoms, the aryl alkylene group of 30 carbon atoms or 20 carbon atoms (comprises aryl alkylene group unsubstituted and that replace; wherein moieties aryl alkylene group can be a straight chain, and side chain is saturated; unsaturated; and/or cyclic and heteroatoms wherein, as oxygen; nitrogen; sulphur, silicon, phosphorus; can or can not be present among one of the moieties of aryl alkylene group and aryl moiety or both with similar atom); but the number of carbon atom can as benzyl or analogue, or (iv) have at least 7 carbon atoms in some embodiments outside these scopes; 12 carbon atoms or 18 carbon atoms; have in some embodiments and be no more than about 55 carbon atoms, (comprise alkyl arylene group unsubstituted and that replace, wherein the moieties of alkyl arylene group can be a straight chain to the alkyl arylene group of 30 carbon atoms or 20 carbon atoms; side chain; saturated, unsaturated, and/or cyclic; heteroatoms wherein; as oxygen, nitrogen, sulphur; silicon; phosphorus and similar atom can or can not be present among one of the moieties of alkyl arylene group and aryl moiety or both), but the number of carbon atom can be outside these scopes; as tolyl or analogue; the alkylidene group of Qu Daiing wherein, arylidene, aryl alkylene; with the substituting group on the alkyl arylene group can be (but being not limited to) oh group; halogen atom, amine groups, imine group; ammonium group; cyano group, pyridine group, pyridine group; ether group; aldehyde group, ketone groups, ester group; amide group; carbonyl group, thiocarbonyl group, sulfate group; sulfonate groups; sulfonic acid group, sulfide group, sulfoxide radicals Phosphonium group; phosphate group, nitrile group, mercapto groups; nitryl group; the nitroso-group group, sulfuryl group, carboxyl groups; anhydride group; azide group, azo group, cyanate radical closes group; isocyano group; the thiocyanato group, thiocyanato group, carboxylate groups; hydroxy-acid group; urethane groups, urea groups, its mixture; and analogue, wherein two or more substituting groups can be combined together to form ring.Organic two suitable anionic examples comprise napadisilate unsubstituted and that replace, the unsubstituted and benzene disulfonate that replaces, and analogue, with and composition thereof.

In another particular, negatively charged ion A can be organic trianion, four negatively charged ion and higher, and oligopolymer and polymer anion, as polysulfonate or multi-carboxylate, or analogue.

For example, the dihalo-fluorescein, as dichlorofluorescein or analogue can with have required R more than one or more ₁, R ₂, R ₃, and R ₄The amine of group, dispensable zinc halide, as zinc chloride or analogue and dispensable non-nucleophilic base, as calcium oxide, zinc oxide, or analogue, pure ground or, mix down if necessary in the existence of solvent.

Amine and dihalo-fluorescein exist with any required or effective relative quantity, be at least 0.9 mol alkali/per 1 mole of dihalo-fluorescein in some embodiments, 0.95 mol alkali/per 1 mole of dihalo-fluorescein or 1 mol alkali/per 1 mole of dihalo-fluorescein, be no more than 20 mol alkali/per 1 mole of dihalo-fluorescein in some embodiments, 10 mol alkali/per 1 mole of dihalo-fluorescein or 2 mol alkali/per 1 mole of dihalo-fluorescein, but this relative quantity can be outside these scopes.

Dichlorofluorescein can be for example available from Aldrich Chemical Co., Milwaukee, WI.The dihalo-fluorescein also can be by fluorescein and PX ₅(wherein X is a fluorine, chlorine, bromine, or iodine), or with tolylsulfonyl halogen, as the reaction of toluene sulfonyl chloride or analogue and prepare.

When using dispensable zinc halide, dihalo-fluorescein and zinc halide exist with any required or effective relative quantity, be at least 2 moles of zinc halides/per 1 mole of dihalo-fluorescein in some embodiments, 2.5 mole zinc halide/per 1 mole of dihalo-fluorescein, or 3 moles of zinc halide/per 1 mole of dihalo-fluoresceins, be no more than 5 moles of zinc halides/per 1 mole of dihalo-fluorescein in some embodiments, 4.5 mole zinc halide/per 1 mole of dihalo-fluorescein or 4 moles of zinc halide/per 1 mole of dihalo-fluoresceins, but this relative quantity can be outside these scopes.

When using dispensable alkali, this alkali exists with any required or significant quantity, is at least 2 equivalent alkali/per 1 mole of dihalo-fluorescein in some embodiments.2.5 equivalent alkali/per 1 mole of dihalo-fluorescein or 3 equivalent alkali/per 1 mole of dihalo-fluorescein, be no more than 10 equivalent alkali/per 1 mole of dihalo-fluorescein in some embodiments, 5 equivalent alkali/per 1 mole of dihalo-fluorescein or 3.2 equivalent alkali/per 1 mole of dihalo-fluorescein, but this relative quantity can be outside these scopes.

If desired, reaction can be carried out under the situation that does not have solvent purely.In addition, if desired, reaction can be carried out in the presence of dispensable solvent.The example of suitable solvent comprises tetramethylene sulfone (tetramethylene sulfone), the N-methylformamide, and dimethyl sulfoxide (DMSO), octanol, or analogue, with and composition thereof.Dispensable solvent can be any required or significant quantity exist, be at least 1 liter/per 0.1 mole of dihalo-fluorescein in some embodiments, 1 liter/per 0.3 mole of dihalo-fluorescein or 1 liter/per 0.35 mole of dihalo-fluorescein, be no more than about 1 liter/per 2 moles of dihalo-fluoresceins in some embodiments, 1 liter/per 1.5 moles of dihalo-fluoresceins or 1 liter/per 1 mole of dihalo-fluorescein, but this relative quantity can be outside these scopes.

The dihalo-fluorescein, amine, dispensable zinc halide, the mixture of dispensable alkali and dispensable solvent is heated to any efficient temperature subsequently, at least 62 ℃ in some embodiments, 150 ℃ or 190 ℃, be no more than 280 ℃ in some embodiments, 220 ℃ or 200 ℃, but temperature can be outside these scopes.

The dihalo-fluorescein, amine, dispensable zinc halide, the mixture of dispensable alkali and dispensable solvent is heated any effective time, at least 5 minutes in some embodiments, 2 hours or 3 hours, be no more than 4 days in some embodiments, 60 hours or 40 hours, although the time can be outside these scopes.

If desired, products therefrom can by reaction mixture to be poured into product wherein be solvable or compatibility and wherein non-required salt by product be insoluble organic water-insoluble and non-water-miscible solvent, as methyl iso-butyl ketone (MIBK), toluene, hexane, heptane, or in the analogue, the solvent that will comprise product subsequently mix in separatory funnel with water and water phase separated and organic phase and purifying.

If desired, crude product can be subsequently by with moisture EDTA washing removal metal-salt, wash with water subsequently and be further purified.If desired, titration or Other Instruments technology can be used for determining whether that as AA (atomic absorption) or ICP (inducing coupled plasma) metal-salt is removed fully.Purified product can separate by distilling all solvents.

Various substituting groups can pass through any required or effective means, for example, are disclosed in the method in U.S. patent 5,847,162 and the U.S patent 1,991,482 and are placed on the ring of tinting material of the present invention.

The carbon atom of additional number can pass through, and for example, selects long-chain amine as reactant and on the structure that centers.The example of these compounds includes, but is not limited to those of following formula

With

Y wherein, R ₁, R ₂, R ₃, and R ₄Have the above identical definition that provides, G is

Or

(1) R has structural formula-C _nH _2n+1The straight chained alkyl group, wherein n is at least 12, (2) R has structural formula-C _nH _2n+1The branched-alkyl group, wherein n is at least 12, (3) R has structural formula-(CH ₂) ₃-O-C _nH _2n+1Ether group, wherein n is at least 11, and analogue, with and open loop, or protonated, or free alkali form and its zwitterionic form.

The carbon atom of additional number also can pass through, for example, at first the corresponding alcohol of preparation and subsequently with these alcohol with, for example, high carbon number acid-respons is made ester, and high carbon number isocyanate reaction is made urethanum, or analogue, or by at first prepare corresponding amine and subsequently with these amine with, for example.High carbon number isocyanate reaction is made urea and on the structure that centers.Such compound includes, but is not limited to those of following formula

With

Or

(1) R is the following formula group

Wherein n is at least 12, and (2) R is the following formula group

Wherein n is at least 12, and (3) R is the following formula group

Wherein n is at least 12, and (4) R is the following formula group

Wherein n is at least 12, and (5) R is the following formula group

Wherein n is at least 12, and (6) R is the following formula group

Wherein n is at least 12, and two R groups on (7) same nitrogen-atoms form a group with following formula with nitrogen-atoms

Wherein n is at least 12, and two R groups on (8) same nitrogen-atoms form a group with following formula with nitrogen-atoms

Wherein n is at least 12, and two R groups on (9) same nitrogen-atoms form a group with following formula with nitrogen-atoms

Wherein n is at least 12, and analogue, with and open loop, or protonated, or free alkali form and its zwitterionic form.

Some object lessons of these compounds comprise those of (a) following formula

With

Wherein n is at least 11, (b) those of following formula

With

Wherein n is at least 12, (c) those of following formula

With

Wherein n is at least 12, (d) those of following formula

With

Wherein n is at least 12, (e) those of following formula

With

Wherein n is at least 12, (f) those of following formula

With

Wherein n is at least 12, (g) those of following formula

With

Wherein n is at least 12, (h) those of following formula

With

Wherein n is at least 12, (i) those of following formula

With

Wherein n is at least 12, (j) those of following formula

With

Wherein n is at least 12, (k) those of following formula

With

Wherein n is at least 12, those of (1) following formula

With

Wherein n is at least 12, (m) those of following formula

With

Wherein n is at least 12, (n) those of following formula

With

Wherein n is at least 12, (o) those of following formula

With

Wherein n is at least 12, (p) those of following formula

With

Wherein n is at least 12, and analogue.

Phase change ink of the present invention comprises phase transformation carrier system or composition.The phase transformation carrier compositions is designed for direct printing mode or indirect or offset printing transfer printing system usually.

Can use any required or effective carrier compositions.Suitable ink carrier examples of material comprises fatty amide, as monoamide, and four acid amides, its mixture, and analogue.The object lesson of suitable fatty amide ink carrier material comprises the stearyl stearylamide, it is dimer acids, quadrol, dimer acidic group four acid amides with stearic reaction product, be dimer acids, quadrol and have dimer acidic group four acid amides of reaction product of the carboxylic acid of at least 36 carbon atoms, and analogue, with and composition thereof.If the fatty amide ink carrier is dimer acidic group four acid amides (be dimer acids, quadrol and acid have the reaction product of the carboxylic acid of at least 36 carbon atoms), this carboxylic acid has general formula

Wherein R is an alkyl group, comprise straight chain, side chain, saturated, unsaturated and cyclic alkyl group, described alkyl group has 40 carbon atoms of at least 36 carbon atoms in some embodiments, described alkyl group has in some embodiments and is no more than 200 carbon atoms, 100 carbon atoms of 150 carbon atoms, but the number of carbon atom can be outside these scopes.But the carboxylic acid market with this structural formula is buied can be for example described and prepare according to the embodiment 1 of U.S. patent 6,174,937.The out of Memory of relevant fatty amide solid support material for example is disclosed in U.S. patent 4,889,560, U.S. patent 4,889,761, U.S. patent 5,194,638, U.S. patent 4,830,671, U.S. patent 6,174,937, U.S. patent 5,372,852, U.S. patent 5,597,856, U.S. patent and 6,174,937 and English Patent GB 2 238 792.

Being suitable for what make the phase change ink carrier material in addition is isocyanic ester deutero-resin and wax, as urethanum isocyanic ester deutero-material, urea isocyanic ester deutero-material, urethanum/urea isocyanic ester deutero-material, its mixture, and analogue.The out of Memory of relevant isocyanic ester deutero-solid support material is disclosed in U.S. patent 5,750,604, U.S. patent 5,780,528, U.S. patent 5,782,966, U.S. patent 5,783,658, U.S. patent 5,827,918, U.S. patent 5,830,942, U.S. patent 5,919,839, U.S. patent 6,255,432, U.S. patent 6,309,453, English Patent GB 2 294 939, English Patent GB 2 305 928, and English Patent GB 2 305 670, English Patent and GB 2 290 793, PCT publication WO 94/14902, PCT publication WO 97/12003, PCT publication WO97/13816, PCT publication WO 96/14364, PCT publication WO 97/33943 and publication WO 95/04760.

Fatty amide material and isocyanic ester deutero-mixtures of material also can be used as the ink-vehicle compositions that is used for printing ink of the present invention.

Be used for other suitable phase change ink carrier material of the present invention and comprise paraffin, Microcrystalline Wax, polyethylene wax, ester type waxes, amide waxe, lipid acid, Fatty Alcohol(C12-C14 and C12-C18), fatty amide and other wax-like materials, sulphonamide material, by different natural origins (as, for example, toll oil rosin and rosin ester) and resin material and a lot of synthetic resins made, oligopolymer, polymkeric substance and multipolymer, as ethylene, ethylene/acrylic acid copolymer, Ethylene/vinyl acetate/acrylic copolymer, the multipolymer of vinylformic acid and polymeric amide, and analogue are from aggressiveness, and analogue, with and composition thereof.One or more these materials also can use with fatty amide material and/or isocyanic ester deutero-material mixing.

In a particular, phase change ink carrier comprises (a) polyethylene wax, its amount in printing ink is at least 25% weight of printing ink in some embodiments, 30% weight or 37% weight, be no more than 60% weight of printing ink in some embodiments, 53% weight or 48% weight, but its amount can be outside these scopes; (b) stearyl stearamide wax, its amount in printing ink is at least 8% weight of printing ink in some embodiments, 10% weight or 12% weight and be no more than 32% weight of printing ink in some embodiments, 28% weight or 25% weight, but its amount can be outside these scopes; (c) dimer acidic group four acid amides, it is dimer acids, quadrol, with have greater than 36 carbon atoms and have the reaction product of long chain hydrocarbon of end hydroxy-acid group, its amount in printing ink is at least 10% weight of printing ink in some embodiments, 13% weight or 16% weight and be no more than 32% weight of printing ink in some embodiments, 27% weight or 22% weight, but its amount can be outside these scopes; (d) derived from the urethane resin of the reaction of 2 Equivalent Hydrogen rosin alcohols and 1 equivalent isophorone diisocyanate, its amount in printing ink is at least 6% weight of printing ink in some embodiments, 8% weight or 10% weight, be no more than 16% weight of printing ink in some embodiments, 14% weight or 12% weight, but its amount can be outside these scopes; (e) be the urethane resin of the affixture of 3 equivalent stearyl isocyanic ester and glycerine-Ji propylated alcohol, its amount in printing ink is at least 2% weight of printing ink in some embodiments, 3% weight or 4.5% weight, be no more than 13% weight of printing ink in some embodiments, 10% weight or 7.5% weight, but its amount can be outside these scopes; (f) antioxidant, its amount in printing ink is at least 0.01% weight of printing ink in some embodiments, 0.05% weight or 0.1% weight and be no more than 1% weight of printing ink in some embodiments, 0.5% weight or 0.3% weight, but its amount can be outside these scopes.

Ink carrier exists with any required or significant quantity in phase change ink of the present invention, be at least 0.1% weight of printing ink in some embodiments, 50% weight or 90% weight, be no more than 99% weight of printing ink in some embodiments, 98% weight or 95% weight, but its amount can be outside these scopes.

Phase change ink of the present invention comprises the following formula colorant compound

Or

This tinting material exists to obtain required color or tone with any required or significant quantity in printing ink, be at least 0.1% weight of printing ink in some embodiments, 0.5% weight, 1% weight, 2% weight or 3% weight, be no more than 20% weight of printing ink in some embodiments, 13% weight or 6% weight, but its amount can be outside these scopes.According to tinting material of the present invention can be in the printing ink unique tinting material or can with other tinting material, as dyestuff, pigment, its mixture and analogue are in conjunction with existence.

In specific embodiments, except tinting material according to the present invention, printing ink of the present invention comprises anthraquinone colorant.The example of suitable anthraquinone colorant comprises solvent red 172, is disclosed in the tinting material of U.S. patent 6,395,078 and U.S. patent 6,422,695 etc.In specific embodiments, anthraquinone colorant is for example according to embodiment XVII, and first to five part is described and prepare.Anthraquinone colorant can be in printing ink of the present invention exists to realize required color with any required or significant quantity, tone, with other characteristic, be at least 1% weight of printing ink in some embodiments, 2% weight or 3% weight, be no more than 20% weight of printing ink in some embodiments, 13% weight or 6% weight, but its amount can be outside these scopes.

In specific embodiments, printing ink of the present invention further comprises the acid of its Ka value greater than the Ka of the carboxylic acid on the tinting material and/or sulfonic acid and/or carboxylate salt and/or sulfonate groups.The object lesson of suitable acid comprises organic sulfonic acid, comprises alkyl benzene sulphonate (ABS) such as tosic acid, Witco 1298 Soft Acid, and analogue, the p-toluenesulphonic acids, spirit of salt, trifluoroacetic acid, methylsulphonic acid, trifluoromethane sulfonic acid, Hydrogen bromide, and analogue, with and composition thereof.Acid exists with any required or significant quantity, be at least 2% weight or 5% weight in some embodiments according to tinting material of the present invention, be no more than 100% weight or 30% weight in some embodiments, but the amount of acid can be outside these scopes according to tinting material of the present invention.

Printing ink of the present invention also can optionally comprise antioxidant.The dispensable antioxidant protection image of ink composite is not oxidized and the protection ink component is not oxidized in printing ink preparation technology's hot spots process.The object lesson of suitable antioxidant comprises NAUGUARD  524, NAUGUARD  76 and NAUGUARD  512, IRGANOX  1010 etc.If exist, dispensable antioxidant exists with any required or significant quantity in printing ink, be at least 0.01% weight of printing ink in some embodiments, 0.1% weight or 1% weight, be no more than 20% weight of printing ink in some embodiments, 5% weight or 3% weight, but its amount can be outside these scopes.

Printing ink of the present invention also can optionally comprise viscosity modifier.The example of suitable viscosity modifier comprises aliphatic ketone, as stearone, and analogue.If exist, dispensable viscosity modifier exists with any required or significant quantity in printing ink, be at least 0.1% weight of printing ink in some embodiments, 1% weight or 10% weight, be no more than 99% weight of printing ink in some embodiments, 30% weight or 15% weight, but its amount can be outside these scopes.

The dispensable additive of other of printing ink comprises finings, as UNION CAMP  X37-523-235, its amount is at least 0.01% weight of printing ink in some embodiments, 0.1% weight or 5% weight, be no more than 98% weight of printing ink in some embodiments, 50% weight or 10% weight, but its amount can be outside these scopes, tackifier, as FORAL  85, the glyceryl ester of hydroabietic acid (rosin) acid, FORAL  105, the pentaerythritol ester of hydroabietic acid, CELLOLYN  21, the staybelite alcohol ester of phthalic acid, ARAXAWA KE-311 resin, the triglyceride level of hydroabietic acid, synthetic polyterpene resin such as NEVTAC  2300, NEVTAC  100, with NEVTAC  80, WINGTACK  86, the synthetic polyterpene resin of modification, and analogue, its amount is at least 0.1% weight of printing ink in some embodiments, 5% weight or 10% weight, be no more than 98% weight of printing ink in some embodiments, 75% weight or 50% weight, but its amount can be outside these scopes, tackiness agent, as VERSAMID  757,759, or 744, its amount is at least 0.1% weight of printing ink in some embodiments, 1% weight or 5% weight, be no more than 98% weight of printing ink in some embodiments, 50% weight or 10% weight, but its amount can be outside these scopes, softening agent, as UNIPLEX  250, with the phthalic ester ester plasticizer of commodity SANTICIZER  by name, as dioctyl phthalate (DOP), phthalic acid two (undecyl) ester, phthalic acid alkyl benzyl ester (SANTICIZER  278), triphenylphosphate, KP-140 , three butoxy ethyl ester of phosphoric acid, MORFLEX  150, dicyclohexyl phthalate, 1,2,4-benzenetricarboxylic acid trioctylphosphine ester, and analogue, its amount is at least 0.1% weight of printing ink in some embodiments, 1% weight or 2% weight, be no more than 50% weight of printing ink in some embodiments, 30% weight or 10% weight, but its amount can be outside these scopes, and analogue.

Ink composite of the present invention has in some embodiments and is not less than 50 ℃, the fusing point of 70 ℃ or 80 ℃ and have and be not higher than 160 ℃ in some embodiments, and the fusing point of 140 ℃ or 100 ℃, but fusing point can be outside these scopes.

Ink composite of the present invention (is not less than 75 ℃ in some embodiments in injection temperature, 100 ℃ or 120 ℃, be not higher than 180 ℃ or 150 ℃ in some embodiments, but injection temperature can be outside these scopes) under melt viscosity be no more than 30 centipoises in some embodiments, 20 centipoises or 15 centipoises, be not less than 2 centipoises in some embodiments, 5 centipoises or 7 centipoises, but melt viscosity can be outside these scopes.

Ink composite of the present invention can prepare by any required or suitable method.For example, ink composition can be mixed together, postheating is at least 100 ℃ in one embodiment, be no more than 140 ℃ temperature in one embodiment, but temperature can be outside these scopes, and stir until obtaining the homogeneous phase ink composite, subsequently printing ink is cooled to envrionment temperature (20-25 ℃ usually).Printing ink of the present invention is solid at ambient temperature.In specific embodiments, in forming technological process, the printing ink that will be in the melt attitude is poured in the mould and with postcooling with solidify and form rod.

Printing ink of the present invention can be used for directly printing the used device of ink-jetting process and is used for (offset printing) indirectly printing ink-jet occasion.Another embodiment of the present invention relates to a kind of technology, comprises printing ink of the present invention is introduced ink-jet printing apparatus, melts this printing ink and the ink droplet of fusing printing ink is ejected on the record base material with the imaging pattern.Directly typography for example is disclosed in U.S. patent 5,195,430 in addition.Another embodiment of the present invention relates to a kind of technology, comprise printing ink of the present invention is introduced ink-jet printing apparatus, melt this printing ink, the ink droplet of this fusing printing ink is ejected on the intermediate transfer element with the imaging pattern, then with printing ink with the imaging pattern therefrom between transferring member be transferred to the final entry base material.In specific embodiments, the intermediate transfer element is heated to above final entry sheet material and the temperature that is lower than the melt printing ink in the printing device.Offset printing or indirect printing technology for example are disclosed in U.S. patent 5,389,958 in addition.In a particular, printing device adopts the piezoelectricity typography, and wherein ink droplet sprays with the imaging pattern by the vibration of piezoelectric vibration device.Printing ink of the present invention also can be used for other thermography technology, as the printing of hot melt acoustic ink jet, the hot ink jet printing of hot melt, continuous logistics of hot melt or deflection ink jet printing and similar printing.Phase change ink of the present invention also can be used for heat extraction and melts and sprays typography outside the ink print technology.

Any suitable substrates or recording sheet be can use, common paper such as XEROX  4024 paper comprised, XEROX image sequence paper, Courtland 4024 DP paper, line notebook paper, silica coated paper such as Sharp Company silica coated paper, JuJo paper, Hammermill laser stamping paper and analogue, transparent material, fabric, textiles, plastics, polymeric film, inorganic substrate such as metal and timber, and analogue.

Embodiment

Example I A

Synthesizing of dichlorofluorescein

With fluorescein (100 grams, 0.331 mole) and PCl ₅(128.5 gram, 0.62 mole) mixture in 650 milliliters of chlorobenzenes is being furnished with and stirs in 1 liter of round-bottomed flask of reflux exchanger and be heated to 140 degrees centigrade.After heating in 6 hours, reflux exchanger is replaced with water distilling apparatus, and distill the POCl that in reaction process, forms ₃And chlorobenzene.Removing all POCl ₃After chlorobenzene, add 300 gram N-Methyl pyrrolidone and the gained mixture under agitation is heated to 100 degrees centigrade, until all thick dichlorofluorescein dissolvings.Solution is introduced in 4 liters of beakers that comprise 1 liter of deionized water subsequently.Brown solid is settled out and is collected on the strainer and be dry in vacuum oven.Final brown solid meets the IR of commercially available dichlorofluorescein, NMR, and TLC.

Also can use other synthesis technique.For example, can adopt pot type technology, wherein a POCl who uses the DMF solvent ₃Intermediate is not distilled but is removed by reacting with methyl alcohol, and methyl alcohol also makes dichlorofluorescein be precipitated as white solid.Also can use and wherein use toluene sulfonyl chloride (a kind of PCl of ratio ₅Not too reactive and corrosion chlorizating agent) method.

Embodiment 1B

Synthesizing of four stearyl tinting materials

Dichlorofluorescein (0.284 mole of 105 gram, preparation are as above), calcium oxide (24 grams, 0.62 mole), ZnCl ₂(116 grams, 0.85 mole) and distearyl amine (288 grams, 0.585 mole; ARMEEN 2HT) mixture in 650 milliliters of tetramethylene sulfones stirs in 1 liter of round-bottomed flask and is heated to 190 degrees centigrade.After heating in 10 hours, the mixture that is coloured to dark magenta is cooled to 120 degrees centigrade and pour in 2.5 liters of methyl-isobutyl isobutyl ketones (MIBK) and be stirred to dissolving fully.

Example I C

The purification of four stearyl tinting materials

The solution of thick four stearyl tinting materials in MIBK is transferred to 4 liters of separatory funnels subsequently.Carry out three moisture EDTA washings (tetra-na salt at the gram of 50 in 1,000 ml water EDTA is used in each washing) subsequently to remove all zinc and the calcium salt in the crude reaction product.The product that is dissolved among the MIBK is stayed the upper strata, and the water on bottom/EDTA inner complex metal waste is dropped.Use deionized water (each 1 liter) washed twice subsequently.At this moment, MIBK solution no longer is pinkish red, but weak orange red.Lack bright magenta this moment and be expressed as and a kind ofly it is believed that closed loop with following formula, or the tinting material of free alkali form

Example I D

The separation of four stearyl tinting materials

Closed loop, the solution of purifying four stearyl tinting materials in MIBK is transferred to 2 liters of round-bottomed flasks with water distilling apparatus subsequently.MIBK and residual water are distilled and product (being a kind of wax of heavy-gravity a little in heat) are transferred to jar and sclerosis.This wax is a kind of scarlet when being cooled to room temperature, hard a little wax.

Example I E

Four stearyl tinting materials protonated

The solid that 250 grams are made in example I D, closed loop, purifying four stearyl tinting materials are transferred to 1 liter of beaker subsequently and add 500 milliliters of MIBK under agitation to dissolve this solid.Witco 1298 Soft Acid with stoichiometry adds this solution and stirred 1 hour subsequently.When adding this acid, observe dark pinkish red tone.Solution is transferred to water distilling apparatus subsequently and removes MIBK.Fusion open loop wax shape tinting material is transferred to aluminium tin subsequently and is cooled to room temperature.This open loop, or protonated, or this tinting material of free alkali form it is believed that to have structural formula

Wherein A is corresponding to the negatively charged ion that is used for protonated acid.The zwitterionic form of this tinting material it is believed that to have structural formula

Repeatedly repeat this technology, wherein Witco 1298 Soft Acid is replaced by following acid: the p-toluenesulphonic acids; Spirit of salt; Trifluoroacetic acid; Methylsulphonic acid; Trifluoromethane sulfonic acid; And Hydrogen bromide.Observe similar results in all cases.

Example II B

Repeat the technology of example I B, just following formula PRIMENE JM-T

Be used for substituting distearyl amine.The amount of PRIMENE JM-T is 2 moles of per 1 mole of dichlorofluoresceins of PRIMENE JM-T/.

Example II C

The product that use obtains in example II B repeats the technology of example I C.It is believed that purified product has following structural formula

Open loop, or protonated, or this tinting material of free alkali form it is believed that to have structural formula

Wherein A is corresponding to the negatively charged ion that is used for protonated acid.The zwitterionic form of this tinting material it is believed that to have following structural formula

Example II D

The product that use obtains in example II C repeats the technology of example I D.

EXAMPLE III B

Repeat the technology of example I B, just UNILIN 425-PA (the formula CH that has ₃(CH ₂) ₃₁-O-CH ₂CH ₂CH ₂NH ₂) compound is used for substituting distearyl amine.The amount of UNILIN425-PA is 2 moles of per 1 mole of dichlorofluoresceins of UNILIN 425-PA/.It is believed that this product has structural formula

This open loop, or protonated, or this tinting material of free alkali form it is believed that to have structural formula

EXAMPLE IV B

Repeat the technology of example I B, just diethanolamine (HN (CH ₂CH ₂OH) ₂) be used for substituting distearyl amine.The amount of diethanolamine is 2.5 moles of diethanolamine/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, and to be N-Methyl pyrrolidone be heated to 125 degrees centigrade and reach 100 hours to substitute tetramethylene sulfone and reaction mixture solvent.

EXAMPLE IV C

The product that use obtains in EXAMPLE IV B repeats the technology of example I C, and just product is introduced in the methyl alcohol and adds enough EDTA to remove all Zn ²⁺And Ca ²⁺Ion.It is believed that purified product has structural formula

EXAMPLE IV C-1

The product that 10 grams obtain in EXAMPLE IV C is added under 120 degrees centigrade in the 23.4 gram octadecylisocyanates, the disappearance that adds 2 dibutyltin dilaurate catalysts (deriving from Aldrich Chomical Co.) after this and reaction system is stirred and heats the isocyanate peak in observing IR.Tetramino ethyl formate rhodamine is introduced into the aluminium pot neutralization and it is believed that to have structural formula

EXAMPLE V B

Repeat the technology of example I B, just following formula N-methyl D-glycosamine

Be used for substituting distearyl amine.The amount of N-methyl D-glycosamine is 2.5 moles of N-methyl D-glycosamines/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc oxide and per 1 mole of dichlorofluorescein to use 1.5 moles of calcium oxide, and to be N-Methyl pyrrolidone be heated to 130 degrees centigrade and reach 7 days to substitute tetramethylene sulfone and reaction mixture solvent.

EXAMPLE V C

The product that use obtains in EXAMPLE V B repeats the technology of example I C, and just product is introduced in the methyl alcohol and adds enough EDTA to remove all Zn ²⁺And Ca ²⁺Ion.It is believed that purified product has structural formula

EXAMPLE V C-1

The product that 10 grams obtain in EXAMPLE IV C is added under 120 degrees centigrade in the 45 gram octadecylisocyanates, the disappearance that adds 4 dibutyltin dilaurate catalysts after this and reaction system is stirred and heats the isocyanate peak in observing IR.Ten urethanum rhodamines are introduced into the aluminium pot neutralization and it is believed that to have structural formula

Example VI B

Repeat the technology of example I B, just following formula 2-piperidines ethanol

Be used for substituting distearyl amine.2-piperidines alcoholic acid amount is 2.5 moles of 2-piperidines ethanol/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, and to be N-Methyl pyrrolidone be heated to 160 degrees centigrade and reach 24 hours to substitute tetramethylene sulfone and reaction mixture solvent.Reaction product is introduced in the water subsequently and filters and wash with water.It is believed that this product has structural formula

Example VI C-1

The product that 10 grams obtain in example VI B is added under 120 degrees centigrade in the 10.7 gram octadecylisocyanates, the disappearance that adds 1 dibutyltin dilaurate catalyst after this and reaction system is stirred and heats the isocyanate peak in observing IR.Diamino acid ethyl ester rhodamine is introduced into the aluminium pot neutralization and it is believed that to have structural formula

Example VII A B

Repeating the technology of example I B, is following formula N, N-dimethyl-1,4-phenylenediamine

Be used for substituting distearyl amine.N, N-dimethyl-1, the amount of 4-phenylenediamine are 2.5 moles of N, N-dimethyl-1,4-phenylenediamine/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, and to be N-Methyl pyrrolidone be heated to 140 degrees centigrade and reach 48 hours to substitute tetramethylene sulfone and reaction mixture solvent.Reaction product is introduced in the water subsequently and filters and wash with water.It is believed that this product has structural formula

Example VII A IB

Repeating the technology of example I B, is following formula N, N-diethyl-1,4-phenylenediamine

Be used for substituting distearyl amine.N, N-diethyl-1, the amount of 4-phenylenediamine are 2.5 moles of N, N-diethyl-1,4-phenylenediamine/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, and to be N-Methyl pyrrolidone be heated to 150 degrees centigrade and reach 96 hours to substitute tetramethylene sulfone and reaction mixture solvent.Reaction product is introduced in the water subsequently and filters and wash with water.It is believed that this product has structural formula

Example I XB

Repeat the technology of example I B, just following formula N-benzyl ethyl alcohol amine

Be used for substituting distearyl amine.The amount of N-benzyl ethyl alcohol amine is 2.5 moles of N-benzyl ethyl alcohol amine/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, and to be dimethyl formamide be heated to 150 degrees centigrade and reach 48 hours to substitute tetramethylene sulfone and reaction mixture solvent.

Example I XC

The product that use obtains in example I XB repeats the technology of example I C, and just product is introduced in the methyl alcohol and adds enough EDTA to remove all Zn ²⁺And Ca ²⁺Ion.It is believed that purified product has structural formula

Example I XC-1

The product that 10 grams obtain in example I XC is added under 120 degrees centigrade in the 9.9 gram octadecylisocyanates, the disappearance that adds 1 dibutyltin dilaurate catalyst (deriving from Aldrich Chomical Co.) after this and reaction system is stirred and heats the isocyanate peak in observing IR.Diamino acid ethyl ester rhodamine is introduced into the aluminium pot neutralization and it is believed that to have structural formula

Embodiment XB

Be used for substituting distearyl amine.The amount of N-benzyl ethyl alcohol amine is 10 moles of N-benzyl ethyl alcohol amine/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, solvent is that excessive N-benzyl ethyl alcohol amine refluxed in oil bath 48 hours to substitute tetramethylene sulfone and reaction mixture, distills excess amine subsequently.

Embodiment XC

The product that use obtains in embodiment XB repeats the technology of example I C, and just product is introduced in the methyl alcohol and adds enough EDTA to remove all Zn ²⁺And Ca ²⁺Ion.It is believed that purified product has structural formula

Embodiment XC-1

In the glass reaction flask, merge the product that 10 grams obtain in embodiment XC, 29.8 gram UNICID  700 (a kind of materials that comprise carboxylic acid with formula R COOH, wherein R is the straight chained alkyl group with average 50 carbon atoms, other that also comprises the highest 25% weight be the functionalized waxes material not), 152 gram dimethylbenzene and the right-toluenesulphonic acids of 0.6 gram.These materials are mixed and be heated to 143 degrees centigrade of reflux temperatures.After 72 hours, reaction is finished.Reaction mixture is cooled to 40 degrees centigrade and filtration subsequently.With filter cake slurrying and in methyl alcohol, refilter twice again to remove remaining dimethylbenzene.Filter cake is dry at ambient temperature in air subsequently.It is believed that this filter cake comprises the following formula tinting material

Wherein n has mean value 50.This open loop, or protonated, or this tinting material of free alkali form it is believed that to have structural formula

Embodiment XIB

Repeat the technology of example I B, just following formula 2-(ethylamino) ethanol

Be used for substituting distearyl amine.2-(ethylamino) alcoholic acid amount is 20 moles of 2-(ethylamino) ethanol/per 1 mole of dichlorofluorescein.In addition, per 1 mole of dichlorofluorescein uses 2 moles of zinc chloride and per 1 mole of dichlorofluorescein to use 1 mole of calcium oxide, solvent is that excessive 2-(ethylamino) ethanol refluxed in oil bath 24 hours to substitute tetramethylene sulfone and reaction mixture, distills excess amine subsequently.

Embodiment XIC

Example I XC-1

The product that 10 grams obtain in example I XC is added under 120 degrees centigrade in the 12.5 gram octadecylisocyanates, the disappearance that adds 1 dibutyltin dilaurate catalyst after this and reaction system is stirred and heats the isocyanate peak in observing IR.Diamino acid ethyl ester rhodamine is introduced into the aluminium pot neutralization and it is believed that to have structural formula

Embodiment XIIB

Repeat the technology of example I B, just the mixture of stearic amine and distearyl amine is used for instead of pure distearyl amine.The amount of stearic amine is that the amount of 1.02 moles of stearic amines/per 1 mole of dichlorofluorescein and distearyl amine is 1.02 moles of distearyl amine/per 1 mole of dichlorofluorescein.

Embodiment XIIC

The product that use obtains in embodiment XIIB repeats the technology of example I C.It is believed that purified product is the mixture of following formula: compound

With

The open loop of these tinting materials, or protonated, or free alkali form it is believed that to have following structural formula respectively

With

Wherein A is corresponding to the negatively charged ion that is used for protonated acid.The zwitterionic form of these tinting materials it is believed that to have following structural formula respectively

With

Embodiment XIID

The product that use obtains in embodiment XIIC repeats the technology of example I D.

Embodiment XIII

Repeat the technology of example I A-IC.Then, the following formula napadisilate affixture that adds 2 moles of naphthalenesulfonate affixtures/per 1 mole of four stearyl tinting material of stoichiometry to the solution of these closed loop purifying four stearyl tinting materials in MIBK

(dinonylnaphthalene disulfonic acid, the 50wt.% solution in isopropylcarbinol, NACURE  155).Stir this solution until producing magenta color fully.Then, solution is transferred to 2 liters of round-bottomed flasks being furnished with water distilling apparatus, and distills MIBK.Product (being a kind of wax of heavy-gravity a little when warm) is transferred to a jar also sclerosis.At room temperature, product is the hard a little wax of a kind of dark magenta/redness, it is believed that to have structural formula

Example II B

Repeat the method for example I B, only be to use Di-Octyl amine (NH ((CH ₂) ₇CH ₃) ₂, derive from Aldrich Chemical Co., Milwaukee, WI) rather than distearyl amine.Di-Octyl amine exists with the amount of 1.95 moles of every mole of dichlorofluoresceins.

Example II C

The product that Application Example IIB obtains repeats the method for example I C.The product that can believe purifying has following general formula

Can believe that the open loop of this tinting material or protonated or free alkali form have following general formula

Wherein A is the negatively charged ion that uses acid corresponding to protonated.The zwitterionic form of this tinting material is considered to have following general formula

Example II D

The product that Application Example IIC obtains repeats the method for example I D.

EXAMPLE III B

Repeat the method for example I B, just react with 2.05 moles of stearylamines of every mole of dichlorofluorescein.

EXAMPLE III C

The product that Application Example IIIB obtains repeats the method for example I C.Can believe that the product behind the purifying has following general formula

The open loop of this tinting material or protonated or free alkali form are considered to have following general formula

Printing ink preparation and test

Embodiment XIV

The preparation of second tinting material

First part

The second pinkish red tinting material is prepared as follows.

In the glass reaction flask, merge 73 gram liters China quinizarin, the colourless quinizarin of 49 grams, 66 gram 4-amino-benzene ethanol, 31 gram boric acid and 780 gram methyl alcohol.Mixed and the heating of these materials refluxes down at 66 degrees centigrade until solvent.

After 16 hours refluxed, reaction was finished, and produced the tinting material of the ethanol-replacement of following formula

Reaction mixture is cooled and filters.The product filter cake is dry at ambient temperature in air.

The spectral intensity of the tinting material of ethanol-replacement is used based on to the spectrophotometry step that tinting material is dissolved in the measurement of tinting material in the solution in the toluene with use Perkin ElmerLambda 2SUV/VIS spectrophotometer measurement light absorption ratio and determine.The spectral intensity of the tinting material of ethanol-replacement is measured as 21,000mL absorbance unit/gram, purity 80% at absorption λ max.

Second section

The tinting material of ethanol-replacement that merging 8 grams are made in the first part of this embodiment in the glass reaction flask, 68 gram glacial acetic acids, 13 gram propionic acid and 2.3 gram diacetyl oxides.These materials are mixed and be heated to 121 degrees centigrade of reflux temperatures.After 4 hours refluxed, reaction was finished and reaction mixture comprises the tinting material of the ethyl acetate-replacement of following formula

Third part

91 grams are comprised from the reaction mixture of the tinting material of the ethyl acetate-replacement of this embodiment second section glass reaction flask of packing into.Mixture is cooled to minimum 30 degrees centigrade.At blended simultaneously, 9 gram bromines being added mixture makes temperature keep below 40 degrees centigrade.Mixture is heated to 40 degrees centigrade subsequently.After 24 hours mixed, reaction was finished.

Reaction mixture is restrained in the deionized water by cold soaking to 234 subsequently and is cooled to room temperature.Reaction mixture is filtered subsequently.Filter cake by slurrying again and in deionized water twice filtration to remove most of remaining acetate.Filter cake is dry in 60 degrees centigrade of stoves subsequently.This filter cake comprises the mixture of tinting material of the ethyl acetate-replacement of following formula bromination

The spectral intensity of the tinting material of bromination ethyl acetate-replacement is used based on the spectrophotometry step to the measurement of tinting material in the solution, by tinting material being dissolved in the toluene and using Perkin Elmer Lambda 2SUV/VIS spectrophotometer measurement light absorption ratio to determine.The spectral intensity of the tinting material of the ethyl acetate-replacement of bromination is measured as 15,000mL absorbance unit/gram at absorption λ max.This spectral intensity is represented purity 60%.

The 4th part

The tinting material of the ethyl acetate-replacement of the bromination that merging 18 grams are made in this embodiment third part in the glass reaction flask and the mixture of its salt, 72 gram N-N-methyl-2-2-pyrrolidone N-s, 4 gram sodium hydroxide and 4 restrain deionized waters.These materials are mixed and be heated to 60 degrees centigrade.After 3 hours, reaction is finished.

Reaction mixture is restrained in the deionized water by cold soaking to 234 subsequently and is cooled to room temperature.The adding glacial acetic acid reaches the pH6-7. reaction mixture until solution and is filtered subsequently.Filter cake by slurrying again and in deionized water twice filtration to remove most of remaining N-N-methyl-2-2-pyrrolidone N-.Filter cake is dry in 60 degrees centigrade of stoves subsequently.This filter cake comprises the tinting material of ethanol-replacement of the bromination of following formula

The spectral intensity of the tinting material of the ethanol-replacement of this bromination is used based on the spectrophotometry step to the measurement of tinting material in the solution, by in the equal blend thing that tinting material is dissolved in toluene and tetrahydrofuran (THF) and use Perkin Elmer Lambda 2SUV/VIS spectrophotometer measurement light absorption ratio to determine.The spectral intensity of the tinting material of the ethanol-replacement of bromination is measured as 16,000mL absorbance unit/gram absorbing material (λ max).This spectral intensity is represented purity 60%.

The 5th part

The tinting material of bromination alcohol-replacement that merging 16 grams are made in this embodiment the 4th part in the glass reaction flask, (have formula R a kind of comprising to 31 gram UNICID  700 ₂The material of COOH institute carboxylic acid, wherein R ₂Be the straight chained alkyl group with average 50 carbon atoms, other that also comprises the highest 25% weight be the functionalized waxes material not), 152 gram dimethylbenzene and the right-toluenesulphonic acids of 0.6 gram.These materials are mixed and be heated to 143 degrees centigrade of reflux temperatures.After 7 hours, reaction is finished.

Reaction mixture is cooled to 40 degrees centigrade and filtration subsequently.With filter cake slurrying and in methyl alcohol, refilter twice again to remove remaining dimethylbenzene.Filter cake is dry at ambient temperature in air subsequently.This filter cake comprises the following formula tinting material

R wherein ₂It is straight chained alkyl group with average 50 carbon atoms.

The spectral intensity of tinting material is used based on the spectrophotometry step to the measurement of tinting material in the solution, by in the equal blend thing that tinting material is dissolved in toluene and tetrahydrofuran (THF) and use Perkin Elmer Lambda 2SUV/VIS spectrophotometer measurement light absorption ratio to determine.The spectral intensity of tinting material is measured as 5,000mL absorbance unit/gram absorbing material (λ max).This spectral intensity is represented purity 40%.

The preparation comprise example I D and IIID tinting material ink composite and in order to contrast purpose, the ink composite that comprises commercially available n-butyl solvent red 172 and commercially available solvent red 49 is as follows.

Printing ink A: (PE 655, have structural formula CH to merge 243.00 gram polyethylene waxs in the stainless steel beaker ₃(CH ₂) ₅₀CH ₃), 122.15 gram stearyl stearamide wax (KEMAMIDE  S-180), be equipped with as U.S. patent 6 108.00 restrain, 174,937 (incorporating it into the present invention as a reference fully) embodiment, 1 described four amide resinss that derive from the reaction of 1 equivalent dimer diacid and 2 equivalent quadrols and UNICID  700 (a kind of carboxylic acid derivative of long-chain alcohol) at this, be equipped with as U.S. patent 5 65.45 restrain, 782,966 embodiment, the 1 described urethane resin that derives from 2 equivalent ABITOL  E hydrogen rosin alcohols and 1 equivalent isophorone diisocyanate, be equipped with as U.S. patent 6 23.00 restrain, 309,453 embodiment 4 are described to be the urethane resin and 1.10 gram NAUGUARD , 445 antioxidants of the affixture of 3 equivalent stearyl isocyanic ester and glycerine-Ji alcohol.These materials are melted in together under 135 degrees centigrade of furnace temperatures, and subsequently by in temperature control jacket, stirring 135 degrees centigrade of following blend 0.2 hour.Adding 22.98 subsequently to this mixture restrains fully as the described four stearyl tinting materials of embodiment ID, 17.66 gram substandard products chromatic colorant agent (preparation as first to the 5th part of this embodiment as described in), with 3.20 gram dodecyl phenyl-hydrogen-sulfates (DDBSA, Bio-soft S-100).After stirring other 2 hours, use Whatman#3 filter paper under 15 pounds/square inch of pressure, to filter the MOTT  device that is heated the product color ink that so forms.Filtering phase change ink is introduced in the mould and solidifies and forms the printing ink rod.The product form and aspect sensitive ink of so making has viscosity 10.49 centipoises of for example measuring under 140 degrees centigrade by rheology awl-plate viscometer, for example use 85 degrees centigrade and 103 degrees centigrade of the fusing points that DuPont 2100 calorimeters measure by differential scanning calorimetry, 19 degrees centigrade of glass transformation temperatures (Tg), with the spectral intensity 1 under 552 nanometers, 023 milliliter of light absorption ratio/gram, the latter is by using based on the spectrophotometry step to the measurement of tinting material in the solution, by solid ink being dissolved in the n-butanols and using Perkin Elmer Elmer Lambda 2SUV/VIS spectrophotometer measurement light absorption ratio to determine.

Printing ink B: printing ink B is according to the similar fashion preparation that is used to prepare printing ink A, but use is as the described different ingredients that is used for ink composite of following table.The performance of printing ink B is used with being used for the same procedure of printing ink A and is obtained.It is as shown in the table, and the main difference between printing ink A and the printing ink B is tinting material and the relative concentration of DDBSA in printing ink.The viscosity of printing ink A and printing ink B is substantially the same.

Printing ink C: printing ink C is by being used to describe the prepared of printing ink A, and just the distearyl tinting material from EXAMPLE III D is used for the four stearyl tinting materials of alternate embodiment ID and does not use the performance use of DDBSA. printing ink C to obtain with being used for the same procedure of printing ink A.

Printing ink D and E: these printing ink are by being used to describe the prepared of printing ink A, and just the distearyl tinting material from EXAMPLE III D is used for the four stearyl tinting materials of alternate embodiment ID and does not use the performance use of DDBSA. printing ink D and E to obtain with being used for the same procedure of printing ink A.Printing ink D and E use with the given identical tinting material of printing ink C but the distearyl tinting material with higher relative concentration, shown in the result of high spectral intensity.

Printing ink F (contrast):, only be to use commercially available SR49 and n-butyl SR172 to substitute from the tinting material of example I D and the substandard products chromatic colorant agent of in first to the 5th part of this embodiment, making by being used to describe a kind of printing ink of prepared of printing ink A.The performance of printing ink F is used with being used for the same procedure of printing ink A and is obtained.

Printing ink G (contrast):, only be to use the alternative tinting material of commercially available SR49 from example I D by being used to describe a kind of printing ink of prepared of printing ink A.The performance of printing ink G is used with being used for the same procedure of printing ink A and is obtained.

Printing ink H: by being used to describe a kind of printing ink of prepared of printing ink A, only be to use the tinting material of in embodiment XIII, making to be used for alternative tinting material from example I D, dinonylnaphthalene disulfonic acid (the 50wt.% solution in isopropylcarbinol, NACURE 155) be used for substituting DDBSA and do not use time tinting material.The performance of printing ink H is used with being used for the same procedure of printing ink A and is obtained.

Following table has gathered the amount (the weight percent numerical value that provides) of the composition and the composition of various printing ink therein in table:

Composition	Printing ink A	Printing ink B	Printing ink C	Printing ink C	Printing ink E	Printing ink F	Printing ink G	Printing ink H
Composition	Printing ink A	Printing ink B	Printing ink C	Printing ink C	Printing ink E	Printing ink F	Printing ink G	Printing ink H	??POLYWAX	40.06	40.16	44.62	43.81	42.99	41.83	45.67	38.68
??S-180	20.14	19.38	13.18	13.18	12.93	19.26	13.17	17.05	??POLYWAX	40.06	40.16	44.62	43.81	42.99	41.83	45.67	38.68
??S-180	20.14	19.38	13.18	13.18	12.93	19.26	13.17	17.05	Four acid amides	17.81	17.82	19.36	19.00	18.64	20.36	19.04	23.56
Urethane resin 1 ^*	10.79	12.47	10.42	10.42	10.22	10.13	10.68	10.45	Four acid amides	17.81	17.82	19.36	19.00	18.64	20.36	19.04	23.56
Urethane resin 1 ^*	10.79	12.47	10.42	10.42	10.22	10.13	10.68	10.45	Urethane resin 2 ^**	3.79	4.26	8.00	7.90	7.75	5.56	8.09	5.76
Example I D tinting material	3.79	2.61	---	---	---	---	---	---	Urethane resin 2 ^**	3.79	4.26	8.00	7.90	7.75	5.56	8.09	5.76
Example I D tinting material	3.79	2.61	---	---	---	---	---	---	EXAMPLE III D tinting material	---	?---	2.30	3.57	5.33	---	---	---
Embodiment XVI tinting material	---	?---	---	---	---	---	---	3.56	EXAMPLE III D tinting material	---	?---	2.30	3.57	5.33	---	---	---
Embodiment XVI tinting material	---	?---	---	---	---	---	---	3.56	??SR49	---	?---	---	---	---	0.55	0.46	---
The agent of substandard products chromatic colorant	2.91	2.03	1.93	1.93	1.93	---	1.91	---	??SR49	---	?---	---	---	---	0.55	0.46	---
The agent of substandard products chromatic colorant	2.91	2.03	1.93	1.93	1.93	---	1.91	---	N-butyl SR 172	---	?---	---	---	---	1.01	---	---
??DDBSA	0.53	?1.10	---	---	---	1.11	0.80	---	N-butyl SR 172	---	?---	---	---	---	1.01	---	---
??DDBSA	0.53	?1.10	---	---	---	1.11	0.80	---	??NACURE?155	---	?---	---	---	---	---	---	0.78
??NAUGUARD ??445	0.18	?0.18	0.20	0.20	0.20	0.19	0.20	0.18	??NACURE?155	---	?---	---	---	---	---	---	0.78
??NAUGUARD ??445	0.18	?0.18	0.20	0.20	0.20	0.19	0.20	0.18	Amount to	100.0	?100.0	100.0	100.0	100.0	100.0	100.0	100.0

^*ABITOL E aminocarbamic acid ethyl ester resin

^*Glyceryl alcohol aminocarbamic acid ethyl ester resin

Use XEROX  PHASER 860 printers successfully to be printed on the HAMMERMILL LASERPRINT  paper product color ink of so making, wherein use typography, wherein printing ink at first is ejected on the intermediate transfer element with the imaging pattern, subsequently with this imaging pattern therefrom between transferring member be transferred to the final entry base material.Obtain the solid view field image of resolving power 450dpi * 600dpi by printer, and its color space data are used the suitable calibration standard that is provided by apparatus manufacturer according to the measuring method of regulation in ASTM 1E 805 (standard operating procedure of the color of material or the instrumental method of chromatism measurement) and are obtained on ACS  Spectro Sensor  II colourimeter.In order to verify and quantize the overall color performance of printing ink, take off data is by three look integrations, according to ASTM E308 (standard method of using the CIE system to be used to calculate object color) reduction, calculate 1976 CIE L* (luminance brightness) of every kind of phase change ink sample like this, a* (redness-green), and b* (yellow-blueness) CIELAB value.

Another kind of printing sample uses KPrinting Proofer and produces on HAMMERMILL LASERPRINT  paper.In the method, test printing ink is fused to the printing plate that is set at 150 degree celsius temperature.The roller rod that paper is housed comprises in its surface on the plate that melts printing ink subsequently and rolls volume.Printing ink on the paper is cooled, and obtains three isolating rectangular block images.Therefore the strongest painted square comprises great majority and is deposited on the printing ink on the paper and uses to obtain color value and measure.

Assessment is recorded in following table from XEROX PHASER  with from the colour characteristics of the product color ink printing sample of K-Proofer.Obviously, use a kind of product look of CIE L*a*b* value representation tone printing-ink of the printing ink of making according to tinting material of the present invention.Following table has been listed the viscosity of printing ink under 140 ℃ (degree centigrade, centipoise), the spectral intensity in the n-butanols (SS, the mL*g of printing ink ^-1Cm ^-1) and the light absorption ratio maximum value (Lambda max, λ max, nm) and use to use the CIE L*a*b color coordinates of the printed matter that XEROXPHASER  860 printers or K-proofer obtain:

Printing ink	???η	????SS	?Lambda ?Max	The CIE L of the printed matter of 860 printers ^/a ^/b ^*	The CIE L of K-proofer ^/a ^/b ^*
Printing ink	???η	????SS	?Lambda ?Max		The CIE L of K-proofer ^/a ^/b ^*	????A	?10.49	10.23	????552	??48.7/76.9/-37.7	??---
????B	?10.54	1328	????552	??50.1/69.1/-37.2	??56.3/59.3/-32.5	????A	?10.49	10.23	????552	??48.7/76.9/-37.7	??---
????B	?10.54	1328	????552	??50.1/69.1/-37.2	??56.3/59.3/-32.5	????C	?10.62	1382	????522	??---	??62.2/71.2/-29.9
????D	?10.30	2075	????522	??---	??58.6/75.0/-27.8	????C	?10.62	1382	????522	??---	??62.2/71.2/-29.9
????D	?10.30	2075	????522	??---	??58.6/75.0/-27.8	????E	?10.59	2874	????522	??---	??54.8/78.0/-25.2
????F	?10.53	1686	????555	??---	??---	????E	?10.59	2874	????522	??---	??54.8/78.0/-25.2
????F	?10.53	1686	????555	??---	??---	????G	?10.77	1279	????555	??54.0/76.8/-41.3	??60.9/68.0/42.7
????H	?---	---	????---	??---	??65.3/70.5/-30.0	????G	?10.77	1279	????555	??54.0/76.8/-41.3	??60.9/68.0/42.7

---expression is not measured

Color value in the last table shows, the tinting material of example I D, and the product look color that the tinting material of the tinting material of EXAMPLE III D and embodiment XVI can be good is used for hot melt printing ink, shows as the high a* and the b* value of printed matter.From showing to find out that obviously the color that comprises the printing ink (printing ink A and B) of the present invention's four stearyl tinting materials is bright product look and is similar to the comparative ink of being made by commercially available SR 49 (printing ink G).Be different from relative strong acid of common needs such as DDBSA to show commercial SR 49 tinting materials of its color in the printing ink base-material, the distearyl tinting material of the present invention among the printing ink C-E has great red product look color and need not sour developer.The spectral intensity of printing ink and a* value increase along with its colorant concentration, shown in printing ink C-E.The good tinting material solubleness performance of distearyl tinting material in test printing ink base-material is very high tinting material heap(ed) capacity and the corresponding very high spectral intensity of printing ink C-E.

Embodiment XVIII

Four stearyl tinting materials from example I D are relatively undertaken by detecting the spectral intensity of its printing ink after heating with the thermostability of contrast SR 49 tinting materials.In the method, printing ink is heated in 145 degrees centigrade stove in glass pot continuously.The spectral intensity (amount that relate to soluble colorant in printing ink) of printing ink in the n-butanols is measured as the function of digestion time.Any thermolysis of test tinting material can be observed because of variable color, changes detecting like this in spectral intensity.

Following table provides the spectral intensity of the relative initial value that changes with the elapsed time of printing ink A and comparative ink F sample.Remaining spectral intensity at this with the tolerance of doing the remaining tinting material of not degrading in the printing ink.Colorant inks A obviously compares with comparative ink F has excellent thermostability.

Cooking time (my god)	???1	???2	???7	??11	??15
Cooking time (my god)	???1	???2	???7	??11	??15	Printing ink A	?100.0	?97.1	?86.9	?79.4	?72.7
Printing ink F	?100.0	?94.1	?80.0	?71.1	?63.7	Printing ink A	?100.0	?97.1	?86.9	?79.4	?72.7

Tinting material degraded not only causes the decline (as above shown in the table) of spectral intensity, moves or fades but also can produce non-required color owing to the tinting material decomposition reaction in the printing ink.If tinting material is not heat-staple, these phenomenons all can influence the quality of colour of the printed matter of these printing ink unfriendly.On angle of practical application, it also is important when assessment tinting material thermostability that the overall color of printing ink changes (E that is determined as color value changes).

Heat stability test heats in glass pot by testing printing ink, take a sample subsequently and use K-Proofer with ink printing on HAMMERMILL LASERPRINT paper and the last colour-change of measuring the printed matter of sampling printing ink as the function of time.The colour-change of gained printed matter detects and is expressed as the Δ E of initial relatively CIELAB value by the CIELAB value.Being used to obtain the described method of CIELAB value more than the colour-change basis of every kind of sample determines.Colour-change is determined (Δ E=[(L* according to ASTM D2244-89 (being calculated the standard test methods of aberration by the Instrument measuring color coordinates) ₁-L* ₂) ²+ (a* ₁-a* ₂) ²+ (b* ₁-b* ₂) ²] ^1/2).Printing ink B, the result of C and G provides in following table.Shown in the data in the form, the printing ink B that comprises example I D and the tinting material of EXAMPLE III D compares with the comparative ink G that comprises SR 49 with C has colour stability preferably.

Cooking time (my god)	????0	????1	????3	????5	????7	????9
Cooking time (my god)	????0	????1	????3	????5	????7	????9	Printing ink A	??0.0	??2.5	??4.3	??3.6	??8.3	??10.2
Printing ink F	??0.0	??4.2	??8.5	??10.0	??11.5	??11.7	Printing ink A	??0.0	??2.5	??4.3	??3.6	??8.3	??10.2

Printing ink C and the G Δ E value when heating down for 140 ℃

Cooking time (my god)	?0	?0.8	1.0	3.0	3.1	5.0	6.9	7.0	10.0
Cooking time (my god)	?0	?0.8	1.0	3.0	3.1	5.0	6.9	7.0	10.0	Printing ink B	?0.0	?---	1.8	3.6	---	5.0	---	5.3	---
Printing ink G	?0.0	?2.6	---	---	4.8	---	8.7	---	9.4	Printing ink B	?0.0	?---	1.8	3.6	---	5.0	---	5.3	---

Printing ink B and the G Δ E value when heating down for 136 ℃;---expression is not measured.

Embodiment XIX

Test the tinting material diffusion of the printing ink (printing ink B) of the tinting material that comprises example I D.For relatively, test the comparative ink G that comprises commercial tinting material SR 49 in addition; Two kinds of printing ink are included in the inferior tinting material and the DDBSA of the 1-5 part of embodiment XIV.This spread evaluating method requires to produce the text printed matter of product color ink, and SCOTCH  adhesive tape is adhered on a part of text, checks that then tinting material diffuses to the degree of adhesive material along with the time.Studying the text printing sample subsequently is how to strengthen the diffusion of tinting material along with the time to observe heat.This test simulation when people with SCOTCH  binder tape labeling the practical situation on by the printed matter that printing ink produced that comprises this tinting material the time.The heating printed matter is used for simulating when the condition of printed matter when warm climate is handled or pass through the high speed file handler.

After 45 degrees centigrade heating also at room temperature kept for 6 weeks in 6 days subsequently down, use the printed text region list of the comparative ink G with commercial tinting material SR 49 to reveal the deep diffusion of tinting material to used adhesive tape, cause the edge blurry of text character.For the printing ink B of the tinting material that comprises example I D, the degree of diffusion is significantly but the degree deficiency, and is positioned at the printed text readability more under the adhesive tape.The result shows that the tinting material of example I D is compared with commercial SR 49 has lower diffusion tendency.Although be not limited to any particular theory, it is believed that the long alkyl group in the tinting material of example I D helps to prevent that tinting material from diffusing to the printing ink base-material.

Claims

1. phase change ink composition that comprises phase change ink carrier and following formula colorant compound

Or

R wherein ₁, R ₂, R ₃, and R ₄Be respectively (i) hydrogen atom independently of each other, (ii) alkyl group, (iii) aromatic yl group, (iv) aromatic yl alkyl group, or (v) kiki fang alkyl group, wherein R ₁And R ₂Can be in conjunction with forming ring, wherein R ₃And R ₄Can be combined together to form ring and R wherein ₁, R ₂, R ₃, and R ₄Can be connected respectively on the benzyl ring in the division center, a and b are respectively integer 0,1,2 independently of each other, or 3, c is an integer 0,1,2,3, or 4, each R ₅, R ₆, and R ₇Be (i) alkyl group independently of each other; (ii) aromatic yl group; (iii) aromatic yl alkyl group; (iv) kiki fang alkyl group; (v) halogen atom, (vi) ester group, (vii) amide group; (viii) sulfuryl group; (ix) amine groups or ammonium group, (x) nitrile group, (xi) nitryl group; (xii) oh group; (xiii) cyano group, (xiv) pyridine or pyridine group, (xv) ether group; (xvi) aldehyde group; (xvii) ketone groups, (xviii) carbonyl group, (xix) thiocarbonyl group; (xx) sulfate group; (xxi) sulfide group, (xxii) sulfoxide radicals, (xxiii) phosphine or phosphorus group; (xxiv) phosphate group; (xxv) mercapto groups, (xxvi) nitroso-group group, (xxvii) carboxyl groups; (xxviii) phosphine or phosphorus group; (xxix) azide group, (xxx) azo group, (xxxi) cyanate radical closes group; (xxxii) isocyano group; (xxxiii) thiocyanato group, (xxxiv) isothiocyanate bonding group, (xxxv) urethane groups; or (xxxvi) urea groups, wherein R ₅, R ₆, and R ₇Can be connected respectively on the benzyl ring in the division center,

Be

Or

R ₈, R ₉, and R ₁₀Be respectively (i) hydrogen atom independently of each other, (ii) alkyl group, (iii) aromatic yl group, (iv) aromatic yl alkyl group, or (v) kiki fang alkyl group, prerequisite is R ₁+ R ₂+ R ₃+ R ₄+ R ₅+ R ₆+ R ₇+ R ₈+ R ₉+ R ₁₀In the number of carbon atom be at least 16, each Q is COOH group or SO independently of each other ₃The H group, each Q ^-Be COO independently of each other ^-Group or SO ₃ ^-Group, d are integers 1,2,3,4 or 5, A be negatively charged ion and CA be hydrogen atom or with all Q of bar one ^-Group bonded positively charged ion, prerequisite are if this colorant compound has structural formula

Or

R wherein ₁₂, R ₁₃, R ₁₄, R ₁₅, R ₁₆, and R ₁₇Be respectively (i) alkyl group independently of each other, (ii) aromatic yl group, (i) aromatic yl alkyl group, or (iv) kiki fang alkyl group, (I) or (a) c is an integer 0,1,2, or 3, or (b) d is an integer 1,2,3, or 4 and (II) or (a) R ₁, R ₂, R ₃, and R ₄In three be hydrogen atom; (b) R ₁, R ₂, R ₃, and R ₄In only one be hydrogen atom; (c) R ₁And R ₂It all is hydrogen atom; (d) R ₃And R ₄It all is hydrogen atom; (e) R ₁And R ₃All be hydrogen atom and R ₂And R ₄Be respectively alkyl group or aromatic yl alkyl group independently of each other.

2. according to the phase change ink composition of claim 1, wherein phase change ink carrier comprises monoamide, four acid amides, or its mixture.

3. according to the phase change ink composition of claim 1, wherein phase change ink comprises urethanum isocyanic ester deutero-material, urethanum/urea isocyanic ester deutero-material, or its mixture.

4. according to the phase change ink composition of claim 1, further comprise anthraquinone colorant.

5. according to the phase change ink composition of claim 1, wherein

Be

6. according to the phase change ink composition of claim 1, wherein tinting material has structural formula

Or

7. the phase change ink composition that comprises phase change ink carrier and following formula colorant compound

Or

Wherein A is a negatively charged ion,

Or

Wherein A is a negatively charged ion,

Or

Wherein n is at least 11,

Or

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Or

Or

Wherein n is at least 12,

Or

Wherein n is at least 12

Or

Wherein n is at least 12,

Or

Or

Wherein n is at least 12

Or

Wherein n is at least 50,

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Wherein n is at least 12,

Or

Or

Or

8. a method comprises

(1) in ink-jet printing apparatus, introduces a kind of phase change ink composition that comprises phase change ink carrier and following formula colorant compound

Or

R wherein ₁, R ₂, R ₃, and R ₄Be respectively (i) hydrogen atom independently of each other, (ii) alkyl group, (iii) aromatic yl group, (iv) aromatic yl alkyl group, or (v) kiki fang alkyl group, wherein R ₁And R ₂Can be in conjunction with forming ring, wherein R ₃And R ₄Can be combined together to form ring and R wherein ₁, R ₂, R ₃, and R ₄Can be connected respectively on the benzyl ring in the division center, a and b are respectively integer 0,1,2 independently of each other, or 3, c is an integer 0,1,2,3, or 4, each R ₅, R ₆, and R ₇Be (i) alkyl group independently of each other; (ii) aromatic yl group; (iii) aromatic yl alkyl group; (iv) kiki fang alkyl group; (v) halogen atom, (vi) ester group, (vii) amide group; (viii) sulfuryl group; (ix) amine groups or ammonium group, (x) nitrile group, (xi) nitryl group; (xii) oh group; (xiii) cyano group, (xiv) pyridine or pyridine group, (xv) ether group; (xvi) aldehyde group; (xvii) ketone groups, (xviii) carbonyl group, (xix) thiocarbonyl group; (xx) sulfate group; (xxi) sulfide group, (xxii) sulfoxide radicals, (xxiii) phosphorus or phosphorus group; (xxiv) phosphate group; (xxv) mercapto groups, (xxvi) nitroso-group group, (xxvii) carboxyl groups; (xxviii) phosphine or phosphorus group; (xxix) azide group, (xxx) azo group, (xxxi) cyanate radical closes group; (xxxii) isocyano group; (xxxiii) thiocyanato group, (xxxiv) isothiocyanate bonding group, (xxxv) urethane groups; or (xxxvi) urea groups, wherein R ₅, R ₆, and R ₇Can be connected respectively on the benzyl ring in the division center,

Be

Or

Or

R wherein ₁₂, R ₁₃, R ₁₄, R ₁₅, R ₁₆, and R ₁₇Be respectively (i) alkyl group independently of each other, (ii) aromatic yl group, (i) aromatic yl alkyl group, or (iv) kiki fang alkyl group, (I) or (a) c is an integer 0,1,2, or 3, or (b) d is an integer 1,2,3, or 4 and (II) or (a) R ₁, R ₂, R ₃, and R ₄In three be hydrogen atom; (b) R ₁, R ₂, R ₃, and R ₄In only one be hydrogen atom; (c) R ₁And R ₂It all is hydrogen atom; (d) R ₃And R ₄It all is hydrogen atom; (e) R ₁And R ₃All be hydrogen atom and R ₂And R ₄Be respectively alkyl group or aromatic yl alkyl group independently of each other;

(2) this printing ink of fusion; With

(3) make the fused ink jet on substrate, form image.